Indian Journal of Chemistry

Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical

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CODEN: ICACEC; ISSN: 0376-4710 (Print), 0975-0975 (Online)

 

 

 

 

VOLUME 55A

NUMBER 12

DECEMBER 2016

 

CONTENTS

 

 

1433

 

DNA binding, cytotoxicity and mitochondria-mediated cell apoptosis induction of a new zinc(II) complex of 5-chloro-8-hydroxylquinoline

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Hai-Rong Zhang, Ting Meng, Qi-Pin Qin,
Sheng-Ping Deng*, Qian-Qian Cao, Hong-Hua Han,
Ying-Bo Li, Yun-Liang Zhang, Yan-Cheng Liu*
& Hong Liang

 

 

 

Zinc(II) complex of 5-chloro-8-hydroxylquinoline binds with
ct-DNA via an intercalative mode, and also exhibits DNA cleavage activity. The complex shows lower cytotoxicity than cisplatin towards some tumor cell lines (
NCI-H460, HepG2, HeLa229, T-24) and the normal liver cell line. However, in the case of the BEL-7404 liver tumor cell line, it exhibits high antitumor activity and induced apoptosis with IC50 value (7.04±0.06 μM) lower than that of cisplatin (25.08±0.12 μM).

 

 

 

 

1443

 

Investigations on the binding behavior of competitive ions to a cationic micelle by 1H -NMR studies

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Nazima Sultana

 

 

 

Alkyl carboxylate counterions like Ac-, Pr- and Bu- play a decisive role in exchange of the native counterions from CPC micelle and transform respectively to CPAc, CPPr and CPBu micelle at/or above a particular salt concentration. The overall binding nature of the added counterions on CPC micelle depends on both kosmotropy and hydrophobic effect.

 

GA (1).tif

 

 

 

1449

 

Catalytic oxidation of cyclohexene by α-zirconium phosphate intercalated Mn(Salen) using 70% tert-butyl-hydroperoxide as an oxidant

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S Khare*, R Chokhare, P Shrivastava, J S Kirar &
S Parashar

 

 

 

The heterogeneous catalytic system, a-ZrP.Mn(Salen)/70%TBHP, gives the maximum conversion (85%) in the oxidation of cyclohexene under the optimum conditions of 30 mmol,
10 mmol and 0.1 mmol of 70% TBHP, cyclohexene and
a-ZrP.Mn(Salen), respectively at 80 °C and 6 h of reaction time. The catalyst can be reused for three cycles without appreciable loss of activity.

 

 

 

S. KHARE_Scheme 2.tif

 

 

 

1458

 

Determination of the azo dye, sunset yellow, by using carbon paste electrode modified with molecularly imprinted polymer

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Zhihua Wang*, Yijiang Shan, Lijuang Xu, Guofan Wu & Xiaoquan Lu*

 

 

 

A highly selective voltammetric sensor for sunset yellow using selective molecular imprinted polymers for preparation of carbon paste electrode is reported. The sensitivity of the sensor is improved significantly on modification with multiwalled carbon nanotubes. The MWCNTs/MIP/CPE shows very high recognition ability in comparison with the MWCNTs/NIP/CPE. Under the optimum conditions, the linear relationship
between current and concentration is obtained in the range of 8×10-8 to 1×10-5 mol L-1. The detection limit of the sensor is 2.667×10-8 mol L-1 (S/N = 3).

 

 

 

 

 

Notes

 

1465

 

Catalytic synthesis of benzimidazole derivatives over modified forms of zirconia

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

T E Mohan Kumar, S Z Mohamed Shamshuddin*, Venkatesh & S Reena Saritha

 

 

 

Synthesis and characterization of solid acid catalysts, viz., ZrO2, Mo(VI)/ZrO2 and Pt-SO42-/ZrO2, is reported. Mo(VI)/ZrO2 comprising moderate to strong acid sites as well as bearing the catalytically active tetragonal phase of zirconia, is an efficient and reusable solid acid catalyst for the synthesis of benzimidazoles.
Pt-SO42-/ZrO2 with very strong acid sites loses its activity
when reused.

 

 

 

 

1471

 

Cloud point extraction with mixed micelles of
TX-114/DOSS and derivative spectrophotometry for simultaneous determination of Fe2+ and Co2+ using 2,2′,6′,2′′-terpyridine

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

K Ravi Kumar & P Shyamala*

 

 

 

A new cloud point extraction procedure with derivative spectrophotometry for the simultaneous preconcentration and determination of Fe2+ and Co2+ has been developed. Both Fe2+
and Co2+ metal ions are simultaneously complexed with
2,2′,6′,2′′-terpyridine at a pH 3.8. and extracted into mixed micelles of Triton X-114 and docusate sodium salt. Under optimum conditions, the linear ranges of Fe2+ and Co2+ are 0.373–2.42 µg mL-1 and 3.14–18.86 µg mL-1 respectively. Their corresponding limits of detections are 0.498 ng mL-1 and 4.54 ng mL-1.

Fig. 1 200 dpi.jpg

 

 

1477

Annual Index

 

 

 

Authors for correspondence are indicated by (*)


 

 

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Indian Journal of Chemistry

Vol. 55A, December 2016, pp. 1433-1442

 

 

DNA binding, cytotoxicity and mitochondria-mediated cell apoptosis induction of a new zinc(II) complex of 5-chloro-8-hydroxylquinoline

Hai-Rong Zhanga, b, c, Ting Menga, Qi-Pin Qina, Sheng-Ping Denga, *, Qian-Qian Caoa, Hong-Hua Hana,
Ying-Bo Lia, Yun-Liang Zhanga, Yan-Cheng Liua, * & Hong Lianga, c

aState Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources,
School of Chemistry & Pharmacy, Guangxi Normal University, Guilin, Guangxi, 541004, PR China

Email: ycliugxnu@aliyun.com (Y-CL); zdsys303@126.com (S-PD)

bCollege of Materials and Environmental Engineering, Hunan University of Humanities,
Science and Technology, Loudi, Hunan, 417000, PR China

cCollege of Chemistry and Chemical Engineering, Central South University, Changsha,
Hunan, 410083, PR China

Received 27 January 2016; revised and accepted 18 November 2016

A new zinc(II) complex (1) of 5-chloro-8-hydroxylquinoline (HClQ) has been synthesized and characterized by IR spectroscopy, ESI-MS spectrometry, elemental analysis and single crystal X-ray diffraction analysis. The DNA binding property of complex (1) has been investigated by UV-vis spectroscopy, circular dichroism spectroscopy and agarose gel electrophoresis. The results indicate that complex (1) binds with ct-DNA via an intercalative mode, and also exhibits DNA cleavage activity. The in vitro cytotoxicity of complex (1) has been screened by MTT assay against a series of tumor cell lines as well as HL-7702 normal liver cell line and, compared with that of cisplatin. Complex (1) shows lower cytotoxicity than cisplatin towards both the tumor cell lines and the normal liver cell line, except the BEL-7404 liver tumor cell line. The IC50 value of (1) towards BEL-7404 is 7.04±0.06 μM, which is lower than that of cisplatin (25.08±0.12 μM). This suggests that BEL-7404 is the most sensitive tumor cell line for (1). Complex (1) is found to induce cell apoptosis in the BEL-7404 cells by arresting the cell cycle at the S phase. The antitumor mechanism of (1) involves targeting the mitochondria-mediated pathway, since the ROS release and the cytoplasmic [Ca2+]c increase in the tested tumor cells after incubation with (1). Flow cytometry assay on the cellular level confirms that the dysfunction of the mitochondria (indicated by the loss of mitochondrial membrane potential) and the release of ROS and Ca2+, directly cause the activation of caspase cascade, including caspase-9 as the initiator and caspase-3 as the executor. These results strongly suggest that the central Zn(II) as the coordinating centre plays the key role in enhancing the antitumor activity and actuating the potential apoptotic pathway for this kind of halogenated quinoline derivatives.

Keywords: Coordination chemistry, Halogenated quinoline, Zinc, DNA binding, Cytotoxicity, Cell apoptosis, Apoptosis

 

Indian Journal of Chemistry

Vol. 55A, December 2016, pp. 1443-1448

 

 

Investigations on the binding behavior of competitive ions to a cationic
micelle by 1H -NMR studies

Nazima Sultana

Department of Chemistry, North–Eastern Hill University, Shillong 793 022, India

Email: sultana.nazima47@gmail.com

Received 13 July 2016; revised and accepted 31 October 2016

The binding nature of aliphatic carboxylate ions, viz. acetate, propionate and butyrate, to a cationic micellar surfactant, viz. cetylpyridinium chloride, has been investigated by 1H-NMR spectroscopy. The carboxylate ions are expected to compete with the chloride ion for binding at micellar interface due to the specific ion effect. The counterions, Ac-, Pr- and Bu-, bind to the cetylpyridinium micelle such that the distance of COO- group from the head group of CPC is almost the same for all the three counterions. This implies that as the length of the alkyl chain of the aliphatic carboxylate counterion increases, it stretches deeper into the palisade layer or core of the micelle. Furthermore, the preference of one ion over another for binding at biological interfaces is broadly termed as specific ion effect and micelles are used as models to mimic the biological membrane. Therefore, effect of competitive ions on the micellization of ionic surfactants provides useful information to better understand the effect of specific ions.

Keywords: Surfactants, Micellar solutions, Cationic micelles, Kosmotropic ions, Chaotropic ions,
Binding studies, Carboxylates, Aliphatic carboxylates, Cetylpyridinium chloride

 

Indian Journal of Chemistry

Vol 55A, December 2016, pp. 1449-1457

 

 

Catalytic oxidation of cyclohexene by α-zirconium phosphate intercalated Mn(Salen) using 70% tert-butylhydroperoxide as an oxidant

S Khare*, R Chokhare, P Shrivastava, J S Kirar & S Parashar

School of Chemical Sciences, Devi Ahilya University, Takshashila Campus, Khandwa Road,
Indore, 452 001 (M P), India

Email: kharesavita@rediffmail.com

Received 18 June 2016; accepted 28 November 2016

A heterogeneous catalyst, a-zirconium phosphate intercalated Mn(Salen) complex, abbreviated as {a-ZrP.Mn(Salen)} has been synthesized by the flexible ligand method. The resulting compound is characterized by BET surface area, X-ray diffraction, energy dispersive X-ray analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and atomic absorption spectroscopy. The catalytic activity of a-ZrP.Mn(Salen) has been tested for the oxidation of cyclohexene using 70% tert-butylhydroperoxide as an oxidant. In the oxidation reaction, cyclohexene is oxidized to cyclohexene oxide, cyclohexenol and cyclohexenone. Influence of various reaction parameters, viz., reaction temperature, catalyst concentration, substrate concentration and oxidant concentration are studied. Under the optimized conditions, oxidation of cyclohexene gives a maximum of 85.50% conversion. The major order of selectivity of the product is: cyclohexenone > cyclohexenol > cyclohexene oxide. The catalyst can be reused for three cycles without significant loss of catalytic activity. The heterogeneity of the catalyst has been tested by hot filtration experiment.

Keywords: Catalysts, Heterogeneous catalysts, Manganese catalyst, Oxidation, Salen, a-Zirconium phosphate, Cyclohexene, tert-Butylhydroperoxide.

 

Indian Journal of Chemistry

Vol. 55A, December 2016, pp. 1458-1464

 

 

Determination of the azo dye, sunset yellow, using carbon paste electrode modified with molecularly imprinted polymer

Zhihua Wang*, Yijiang Shan, Lijuang Xu, Guofan Wu, Xiaoquan Lu*

Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu Province,
College of Chemistry & Chemical Engineering, Northwest Normal University
, Lanzhou, 730070 China

Email: zhwang@nwnu.edu.cn (ZW)/luxq@nwnu.edu.cn (XL)

Received 31 August 2016; accepted 25 November 2016

A highly selective voltammetric sensor for sunset yellow is reported. Sunset yellow selective molecular imprinted polymers (MIP) and non-imprinted polymers have been synthesized and used for preparation of carbon paste electrode. The MIP, incorporated in the carbon paste electrode, functions as selective recognition element and pre-concentrator agent for determination of the dye. The sensitivity of the sensor is improved greatly because of the multiwalled carbon nanotubes (MWCNTs). The complete removal of the dye from the polymer was confirmed by the infrared spectra and the differential pulse voltammetry. The MWCNTs/MIP/CPE has been characterized by electrochemical impedance spectroscopy, cyclic voltammetry and DPV. The MWCNTs/MIP/CPE shows very high recognition ability in comparison to the MWCNTs/NIP/CPE. Under the optimum conditions, the linear relationship between current and concentration was obtained in the range from 8×10-8 to 1×10-5 mol L-1. The detection limit of the sensor is 2.667×10-8 mol L-1 (S/N=3).

Keywords: Molecularly imprinted polymer, Azo dyes, Sunset yellow, Carbon paste electrodes,
Multiwalled carbon nanotubes, Voltammetric sensors, Sensors

 

Indian Journal of Chemistry

Vol. 55A, December 2016, pp. 1465-1470

 

 

Catalytic synthesis of benzimidazole derivatives over
modified forms of zirconia

T E Mohan Kumara, b, S Z Mohamed Shamshuddina, b, *, Venkatesha, b & S Reena Sarithaa, b

aChemistry Research Laboratory, HMS Institute of Technology, NH4, Kyathsandra,
Tumakuru 572 104, Karnataka, India

bResearch and Development Center, Bharathiar University, Coimbatore 572 104, India

Email: mohamed.shamshuddin@gmail.com

Received 2 May 2016; revised and accepted 3 November 2016

The solid acid catalysts, ZrO2, Mo(VI)/ZrO2 and Pt-SO42-/ZrO2 have been prepared and characterized for their surface area by BET, total surface acidity by NH3-TPD/ n-butyl amine back titration and crystallinity by powder XRD methods. These solid acid catalysts have been used in the synthesis of various benzimidazole derivatives. The results have been interpreted based on the variation of acidic properties and powder XRD phases of zirconia on incorporation of Mo(VI) or Pt-SO42– ions. Mo(VI)/ZrO2 is found to be an efficient solid acid catalyst for the synthesis of benzimidazoles with up to ~98% yield. These solid acids were found to be reusable up to at least 5 reaction cycles. Plausible mechanism for the formation of benzimidazoles over protonic acid sites of the solid acid catalysts is proposed.

Keywords: Catalysts, Solid acids catalysts, Zirconia, Modified zirconia, Benzimidazoles

 

Indian Journal of Chemistry

Vol. 55A, December 2016, pp. 1471-1475

 

 

Cloud point extraction with mixed micelles of TX-114/ DOSS and derivative spectrophotometry for simultaneous determination of
Fe2+ and Co2+ using 2,2′,6′,2′′-terpyridine

K Ravi Kumar & P Shyamala*

Department of Physical and Nuclear Chemistry & Chemical Oceanography, School of Chemistry,
Andhra University, Visakhapatnam 530 003, Andhra Pradesh, India

Email: shyamalapulipaka06@gmail.com

Received 24 August 2016; revised and accepted 5 December 2016

A new cloud point extraction procedure with derivative spectrophotometry for the simultaneous preconcentration and determination of Fe2+ and Co2+ has been developed. In this method both the Fe2+ and Co2+ metal ions are simultaneously complexed with 2,2′,6′,2′′-terpyridine at a pH of 3.8. The complexes of Fe2+ and Co2+ are then extracted into mixed micelles of surfactants (Triton X-114 and docusate sodium salt). Various parameters such as pH, concentration of the ligand, concentrations of the surfactant, concentration of salt (Na2SO4), equilibration temperature and time have been optimized. Under optimum conditions, the linear ranges of Fe2+ and Co2+ are found to be 0.373–2.42 µg mL-1 and 3.14–18.86 µg mL-1 respectively. Their corresponding limits of detections are found to be 0.498 ng mL-1 and 4.54 ng mL-1. The proposed method has been successfully applied to the determination of Fe2+ and Co2+ in tap water and sea water. The recoveries were found to be in the range of 98–107%.

Keywords: Analytical chemistry, Derivative spectrophotometry, Cloud point extraction, Mixed micelles, Surfactants, Iron, Cobalt, Terpyridine